Flavoring agent

ABSTRACT

Enhancement of the flavor of foodstuffs is achieved by the addition of an effective flavor-modifying amount of a pyrone of the formula:   WHEREIN EACH OF THE SYMBOLS X and Y represents oxygen or sulfur.

Unite States atent Winter et al.

FLAVORING AGENT Inventors: Max Winter, Geneva; Fritz Gautschi, Vaud; lvon Flament; Max Stoll, both of Geneva, all of Switzerland; Irving M. Goldman, Niantic, Conn.

Assignee: Firmenich & Cie, Geneva,

Switzerland Filed: June 24, 1974 Appl. No.: 482,818

Related US. Application Data Division of Ser. No. 243,866, April 13, 1972, which is a division of Ser. No. 70560, Sept. 8, 1970, Pat. No. 3,702,253. which is a continuation of Ser. No. 543,069, April 18, 1966, abandoned, which is a continuation-in-part of Ser. No. 452,342, April 30, 1965, abandoned.

US. Cl. 426/535; 426/594; 426/589;

426/536; 260/327 TH; 260/3451; 260/3459 Int. Cl A231 1/26 Field of Search 426/65, 175, 221, 193,

1 Aug. 19, 1975 Primary ExaminerRaymond N. Jones Assistant Examiner-Esther L. Massung Attorney, Agent, or FirmHoward J. Newby; Thomas V. Sullivan; Bruno P. Struzzi 5 7 ABSTRACT Enhancement of the flavor of foodstuffs is achieved by the addition of an effective flavor-modifying amount of a pyrone of the formula:

wherein each of the symbols X and Y represents oxygen or sulfur.

16 Claims, N0 Drawings FLAVORING AGENT This is a division of application Ser. No. 243,866 filed Apr. I3, 1972, which is a division of application Ser. No. 70,560 filed Sept. 8, 1970, now US. Pat. No. 3,702,253; which latter application is a continuation of now-abandoned application Ser. No. 543,069 filed Apr. I8, 1966, which is a continuation-inpart of nowabandoned application Ser. No. 452,342 filed Apr. 30, 1965.

The invention relates to flavor agents in general. More particularly the invention relates to chemical compounds or compositions which have been found to have utility in the alteration of flavor or flavor characteristics of substances, whether naturally occurring or synthetic. Still more particularly the invention relates to a group of chemical compounds which have been found to be useful in the area of flavor-note alteration, whether by the enhancement of flavors or flavor-notes that are characteristic in a substance, by the alteration of a flavor or a flavor-note from a less to a more desirable one, or by the complete or partial masking ofa flavor or flavor-note.

As is generally recognized by those familiar with the art, the science of flavor technology is an extremely complex one. Although much is known about flavor and flavor technology there is still a great deal to be learned in the field and the body of scientific literature is being rapidly expanded by those working in the area. The technology of flavor synthesis and blending of various flavor elements to achieve certain desirable results is of great commercial importance at the present stage of industrial advance. Commercial production of consumer goods from synthetic starting materials is becoming more and more common, and desirable, as world population continues to increase its demands upon the finite capacity for the production of natural products. Industry is also continually seeking means of upgrading natural products methods of altering or enhancing the qualities of taste of less desirable natural products Usually more abundant into more desirable product qualities. Often, for example, a product can be made commercially attractive only by masking or blanking out an undesirable flavor component. Formcrly, before the advent of the flavor chemist and his technology, this unit of production would have been lost, or at least, would have had to have been reprocessed to a useable quality. By the use of specifically designed flavoring agents, however, the undesirable flavor note can be eliminated or masked with another desirable one, and the expensive and timeconsuming reprocessing step eliminated or the production batch saved for use. Too, it is common in some segments of the industry, particularly the food industry, to add flavor agents to production units to enhance or bring out a desirable flavor characteristics of products and by so doing to render the product more desirable from a consumer preference standpoint.

It is the object of this invention therefore, to provide the flavor technologist with additional tools for his use in the alteration of food flavors, whether it be flavor or flavor-note alteration generally or the enhancement or improvement of flavor or flavor notes specifically.

It is a further object of the invention to furnish a group of chemical compositions which have utility in the technology of flavor alteration, whether added to solid or liquid compositions for human consumption, and which may be used in either solid or liquid form.

A further object of the invention is to describe several groups of chemical compounds having desirable utility as flavor agents which may be prepared synthetically, thus enabling the food technologist to alter or enhance his product without drawing upon a natural product for the flavor agent.

A still further object of the invention is to describe a group of chemical compounds capable of synthesis from readily available organic substances which may be used singly or in combination to alter the flavor or flavor notes of compositions for food use, whether used in micro-quantities such as parts-per-million or in larger quantities, as the dictates of the end results may require.

Other objects will become apparent to those skilled in the art as the description proceeds.

Thus, in accordance with the concept of the instant invention, there is set out below a series of groups of compounds which have been found to have utility as flavor agents and to represent valuable materials to the food technologist who wishes to alter the flavor components of foods or food products either liquid foods or beverages, such as fruit and vegetable juices, milk, coffee, tea, cocoa, chocolate, and the like or solid foods such as cereals, flours, confections, vegetables, meats, etc. The flavor agents may be used either in liquid or solid form and are used in quantities designed to give the desired results, as will be more clearly explained as the description proceeds.

The chemical compounds which have been found to have utility as flavor agents may be generally classified according to the following groups:

I. Diphenyls II. Substituted Napthalenes III. Furan Hydrocarbons IV. Thiophene Hydrocarbons V. Pyrrole Hydrocarbons VI. Pyridine Hydrocarbons VII. Pyrazine Hydrocarbons VIII. Aliphatic and Aromatic Alcohols IX. Furan Ethers X. Thiophene Ethers XI. Thiazole Alcohols XII. Pyridine Ethers and Alcohols XIII. Pyrazine Ethers and Alcohols XIV. Benzofuran Carbonyl Compounds XV. Thiophene Aldehydes XVI. Pyrrole Aldehydes XVII. Pyrazine Carbonyl Compounds XVIII. Aliphatic and Aromatic Ketones XIX. Furan Ketones XX. Thiophene Ketones The above groupings are selected more for reasons of chemical similarity than because of flavor alteration characteristics as will be more specifically described in relation to the more complete definition afforded each particular group.

The flavor agents or flavor modifying compositions of this invention are available to the food technologists in a variety of forms. It is usually preferable to use the agents in the form of a solution, for ease of dilution, exactitude of measurement, efficiency of distribution in the end use, etc. However the chemical nature of the compound, its solubility in acceptable solvents, its stability, and other characteristics may dictate the form in which it is used.

The amounts of the agents used is also subject to wide variation, of course. More concentrated materials, and those with the greatest degree of flavor modifying ability will be used in lesser amounts. Some degree of experimentation is, of course, required to achieve the desired results. A small, but flavor modifying amount, of the agents is blended with the material whose total flavor is to be altered, the amount depending upon the end result desired.

Two different types of methods were used in testing the compounds listed in this specification for their utility as flavor agents, flavor modifiers, flavor alteration agents, flavor-note enhancers, and the like. The first type method (A) served the purpose of determining the intrinsic taste, flavor and aroma of each individual compound. The second type methods (B) and (C) were used for testing the flavorand aroma-modifying or -enhancing effects of the compounds hereinafter listed on coffee products and more particularly on spray-dried soluble coffee products commercially known as instant coffee.

Method A.

The vehicle used for testing the flavor compounds was a 65 percent solution of cane sugar in tap water. The flavor compounds were incorporated in this sugar syrup in the form of 1 percent or 1 per 1,000 by weight solutions in 96 percent ethyl alcohol. The concentration of the flavor compounds in the sugar syrup varied between about 0.005 and 5 g. for 100 liters of syrup according to the varying strength of flavor compounds. Samples of each flavored sugar syrup were submitted to the members of the tasting panels. After tasting the samples each member had to give an evaluation of each flavor compound in terms of descriptive words.

In the evaluation of materials for the alteration or enhancement of coffee flavor or of coffee flavor notes it is essential that the equipment used, coffee pots, cups, spoons, measuring equipment, etc. be absolutely clean prior to use.

Method B.

The coffee base was prepared by dissolving l g. of a commercial spray-dried soluble coffee in boiling water. A sufficient number of pots was prepared to provide one pot for each flavor agent to be evaluated plus one control. The flavor agent was added to the coffee base in the form ofa 1 percent or 1 per 1,000 by weight alcoholic solution at concentrations varying between 0.005 and 5 g. of flavor agent for 100 liters of coffee base. The measured quantity of the flavor agent was added to a pot of the coffee base material, stirred well, and poured immediately into cups for the organoleptic evaluation. The taste tests were made within a short time (not more than minutes) after the final composition to be tested was prepared.

The organoleptic evaluation involved grading a series of cups that were coded, the taster merely rating the coded cups against the standard or control which did not contain the flavor agent. The standard was placed at the first position in a series of cups. The tasters were asked to ascertain whether or not there existed differences in the flavor of the samples to be tested as compared with the control. The tasters were furthermore asked to describe and characterize the various flavor notes and types determined.

Method C.

Using boiling Crystal Spring Water, to provide a clean starting taste, a 1.35 percent solution of relatively bland tasting commercially available spray-dried soluble coffee was prepared. The containers used preferably the lower portion of a glass coffee maker was absolutely clean, as was the other equipment used, e.g., cups and spoons.

A sufficient number of containers, or pots, were used to accomodate each flavor fraction to be studied, plus one control. The flavor fraction was measured carefully with a micro-syringe, adding from 2 to microliters of the flavor fraction per pot. The mixture of coffee solution and flavor fraction was stirred and immediately poured into cups for tasting. At least 5 experienced tasters are used. The tasting should begin at least within 15 minutes after the solution is prepared. If not, the solution should be discarded and fresh solution prepared.

The cups are coded and the samples are not identified. A standard sample is included in which no flavor fraction has been added. The taster is asked to identify and describe the flavor enhancement or modification noted.

In the following specific description of the compounds of the Groups listed above (I XXXVIII) there is first given the structural formula followed by a list of members of the group which have been found to have outstanding utility in the concept of this invention. Immediately following the chemical name of each member there is given the commercial source or a literature reference giving a method for its preparation. Commercially available products will be identified by the abbreviation o.a., and may be obtained from FLUKA, A.G., Buchs S.G., Switzerland; ALDRICH CHEM. CO., Milwaukee, Wis.; DR.F. RASCHIG GMBH, Lugwigshafen a. Rh., West-Germany; or K and K LABORA- TORIES INC., Plainview, NY. 11803.

In those instances wherein new compounds are described a detailed method of preparation is given following the list of the group members. New compounds will be identified by the abbreviation n.c.

The results of the organoleptic evaluation tests are set out in the group of TABLES following the detailed description of the groups of compounds I. Diphenyls In this first group of compounds are included those having the structural formula:

R w W wherein R is hydrogen or an alkyl group, e.g. methyl. Typical compounds are:

Organoleptic evaluations as flavor agents are described in TABLE 1 below.

11. Substituted Naphthalenes Compounds in this group are those having the general formula:

wherein R is hydrogen or an alkyl group, e.g., methyl or ethyl,

at least one of the Rs being an alkyl group. Typical compounds include:

The compounds enumerated above were evaluated organoleptically and gave the results set out in TABLE ll below.

III Furan Hydrocarbons The compounds of this group which have utility according to the inventive concept are selected from the class of compounds having the general formula:

[I CHOCH-H wherein R is hydrogen or an alkyl group containing from 1 to 3 carbon atoms; compounds of the formula:

wherein R is hydrogen or an alkyl or an alke'nyl group of from 1 to 3 carbon atoms, provided that the sum of the carbon atoms of the substituent groups does not exceed 3; and compounds of the formula:

II II 1 2 wherein R, is hydrogen or a methyl group and wherein R is -CH2L o ILR.

R being hydrogen or a methyl group such that R and R are not both hydrogen.

Specific compounds included in this group of compounds are:

'. 2-vinyl-furan Ball. 1947. 453

The new compounds included in Group [II can be prepared by the methods described below.

(2) f. 2-lsopropenyl-benzofuran. According to the method described in J.A.C.S. 73, 754 1951) 2-acetylbenzofuran is reacted with methyl-magnesium bromide to form 2-(2-hydroxy-isopropyl)-benzofuran which is converted to its acetate. Pyrolysis of the acetate yields 2-isopropyl-benzofuran of b.p. 8l83C./0.001 mm. Hg.

(2) h. 7-Ethyl-benzofuran is prepared by the method described in J. Chem. Soc. 1920, 1534, but using 0- ethylphenol instead of o-cresol. The MS. of the product thus obtained shows the following ion peaks with the relative intensities given within brackets: 131 percent), 146 (38 percent) and 77 (10 percent).

(2) i. 2,7Dimethyl-benzofuran. 7-Methylbenzofuran (of. compound (2) g.) is subjected to a WILSMEYER reaction to form 7-methyl-benzofuran- 2-aldehyde which is converted into 2,7-dimethylbenzofuran by a WOLFF-KISHNER reaction by the method described in Bull. Soc. Chim. France 29, 1875 (1952). The product thus obtained has the following peaks in its MS: 146 (100 percent), (92 percent) and 131 (32 percent).

Organoleptic evaluations of this group of compounds are set out in TABLE III below.

IV. Thiophene Hydrocarbons The thiophene hydrocarbons having utility in accordance with the instant inventive concept are those compounds described by the structural formula:

R and R are hydrogen, methyl, ethyl, vinyl or propy the compound of the formula:

the compounds of the formula:

(5) Dogma, 11 x wherein R and R are hydrogen or methyl groups, and

wherein X is oxygen or sulfur; the compounds of the formula I T h s a n1 R and R are hydrogen or methyl groups, and the compounds of the formula wherein wherein X is oxygen or sulfur and R is hydrogen or a methyl group, provided that, if X represents oxygen, R is methyl.

Organoleptic test evaluations are set out in TABLE V below.

VI Pyridine Hydrocarbons The compounds of this group which have utility according to the instant concept are to be described as falling under the general formula:

2 r 1 5 (1) R a a 1 wherein N R and R represent hydrogen or alkyl groups. wherein Typical compounds of this class of compounds are: R R and R are hydrogen, alkyl, e.g. methyl, ethyl,

( l a. Z-methyl-thiophene 0.21. b. B-methyl-thiophene c.a. c. Z-ethybthiophene (2.8. d. 3-ethyl-thiophene Ball. 1955, 424 e. 2-propyl-thiophene .I.A.C.S. '70, 39], Bull.

1955. 36] f. 2-vinyl-thiophene Bull. 1955, 424 g. 3-vinyl-thiophene Bull. [955, 424 h. Z-methyl-4-ethyl-thiophene J.A.C.S.75, 989 1953) i. 2-methyl-5-ethyl-thiophene J.A.C.S.75, 989 1953) j. 2-methyI-S-propyl-thiophene J.A.C.S.75, 989 1953) k. 2,5-dimethyl-thiophene era. (2) u. 2,3,3, 2-thiophenothiophcne Soc. I953, 1837 (3) a. 2,2-dithienyl-methune J.A.C.S.73. 1270 (195i) h. 5,4"dimethyl-2.2-dithienylmethane J.A.C.S.73, 1270 195] c. 2-furyl-2-thicnyl-methane CA. 57, 9776f 1962) d. (S-mcthyl-Zthienyl)-2furyl-methune CA. 57, 9776f 1962) (4) a. 2.2-dithienyl J.A.C.S.78, 1958 (I956) h. 5.5-dimethyl-2,2-dithienyl-methune J.A.C.S.78, 1958 (1956) (5) a. benzothiophene cxu.

b. Z-methyl-henzothiophcne J.A.C.S.74, 664 1952) Organoleptic evaluations of these compounds are set isobutyl, alkenyl groups, e.g. vinyl, propenyl; aryl out in TABLE IV below. groups; or aralkyl groups; provided that the symbols R R and R are not all hydrogen. Pyrrole Hydrocarbons Typical compounds include: Compounds of this group have the general formulae:

( l a. Z-methyl-pyridine c.a. b. 3-methyl-pyridine ca. (1) l c. 3-ethyl-pyridine ca (1. Z-aIIyI-pyridine Bull. 420, 1955) e. 4-isohutyl-pyridine Bull. 420. 1955) N f. 2-( l )-propenyl-pyridine Ann. 247, l (1888) h g. 4-(l)-propenyl-pyridine Ann. 247, 1 (1888) h. Z-methyI-SethyI-pyridine c.a. wherein i. 2,3-dimcthyl-pyridine 0.21. 6O 2,4dimeth lridine c.u. R is alkyl, e.g., ethyl, amyl, isoamyl, or alphamethyl- 25 dimeh; gridine UL utyl, and 1. 2.6-dimethyl-pyridine cu. m. 3,4-dimethyl-pyridine c.u. n. 3,5-dimethyl-pyridine ca. I o. Z-vinyl-pyridine c.u. (2) p. 4-methyl-pyr dlne c.u. q. 2-methyl6-v1nyl-pyridme can. l r. 4-phenyl-pyridine e11. C R s. 4-benzyl-pyridine on. 2 t. Lhenzyl-pyridinc c.u. X u. 2-muthyl-S-ethyl-pyridine on.

Organoleptic evaluations are set out in TABLE VI below.

Vll Pyrazine Hydrocarbons This important group of compounds have been found to have exceptional utility as flavor agents in accor- 3) I dance with the instant inventive concept. Compounds of the group have the general formulae:

l() N X wherein (1) bon atoms,

N wherein (5) a} R is hydrogen, alkyl, l-pyrrolyl or Zthienyl; and R R is alkyl or alkenyl,

N wherein R R (2) R carbon atoms, and

R 6 wherein 3O( R R and R are alkyl groups having from 1 to 5 car- N hon atoms,

wherein wherein R R and R are hydrogen or methyl groups,

R and R are alkyl groups containing from 1 to 3 car- R,, R R and R are groups containing from 1 to 6 R is methyl or ethyl and R is alkyl or alkenyl with C1 IO C Compounds of this group which are of special interest include:

Z-methyl-B-ethyl-pyrazine 2-methyl-3-isobutyl-pyrazine 2-methyl-S-propyl-pyrazine 2-methyl-3-isopropyl-pyrazine 2methyl-3-hutyl-pyrazine 2 methyl-3-(thienyl-2)-pyrazine Z-ethyLpyrazine Z-pmpyI-pyrazine 2-isopropyl-pyrazine 2vinyl-pyrazinc 2-isopropenyl-pyruzine Z-methyl-B-vinyl-pyruzinc trimethyl-pyrazmc n.c. Ber. 40, 4855 (1907) n.c, J Org.Chem.26, 3379 [961 J.Org.Chem.26, 3379 I961 J.Org.Chem.26 3379 I961 I.Org.Chem.26, 3379 1961 n.c. J.AC,S. 72, 844 I950) (3) S-methyl-quinoxaline Organoleptic evaluations are set out in TABLE Vll Z-mcthyl-quinoxulinc fi-methyl-quinoxaline 2,3-dimethyl-quinoxaline 2-methyl-3-cthyl-quinoxaline 2.3-diethyl-quinoxaline 2-methyl-3-propyl-quinoxaline Z-methyl-3-isopropyl-quinoxaline 2-rnethyl-3-butyl-quinoxaline Z-methyl-3-isobutyl-quinoxaline 2-methyl-3-amyl-quinoxaline 2-ethyl-quinoxaline 2-methyl-6-ethyl-pyrazine below The new compounds of this Group Vll can be prepared as follows:

Ann.237, 336 I887) ()rg.Synth.30.86 1950) Ann. 237.33%)(1887) Ber. 40, 4852 (1907) Ber. 22. 526 1889) J.A.C.S.79,l7l2 (1957) J.Cl1em.Soc. 1946, 54 J.Chem.Soc. 1953, 2822 n.c. J.Chem.Soc. 1943 322 J.Chem.Soc. 1953. 2822 11.0 J.Org.Chem. 27. 1355 TLC.

TLC.

lLC.

TLC.

TLC.

l'LL.

l'LC.

Z-methyl-fi-isobutyl-pyrazine 2-methyl-3-propylpyrazine 2-methyl-3-isopropyl-pyruzine The 2,3-disubstituted pyrazines (formula l can be obtained by a method comprising catalytically dehydrogenating with copper chromite the correspondingly substituted dihydropyrazines which, in turn, can be prepared by condensation of ethylene diamine with the corresponding alpha-diketones. By way of illustration the preparation of 2-methyl-3-ethyl-pyrazine is described in more details.

( l) a. 2-Methyl-3-ethyl-pyrazine. In a 3-necked flask equipped with a stirrer, means for cooling and a dropping funnel there was placed 150 g. of ethylene diamine in 500 ml. ether. After cooling to 0C there was slowly added with stirring a solution of 250 g. of ethyl methyl diketone in 500 ml. of ether. After the addition was complete, the temperature was allowed to rise to room temperature and the mixture was heated on a water bath for a few minutes. The material separated into 2 phases and the water phase was discarded. The ether phase was dried with sodium sulfate, the solvent was removed by evaporation and the residue distilled under reduced pressure and an inert atmosphere. There was obtained 192 g. of the dihydropyrazine (62 percent yield), boiling point 6l 65C./ll mm. Hg.

In an apparatus similar to that described by Bouveault in Bull IV, 3, 119 (1908) the dihydro pyrazine was distilled under reduced pressure under nitrogen atmosphere through a column containing copper chromite (Girdler G-l3). The catalyst was heated to 300C electrically and the effluent was passed through a Widmer column to separate the unhydrogenated material.

The product was condensed, dried and redistilled; a 90 percent yield was obtained of a product boiling at 57C./l0 mm. Hg.

The same method as used for compound (1) a. was applied for the preparation of the following compounds:

(1) j. 2-Ethyl-3-vinyl-pyrazine can be prepared from 2-ethyl-3-methyl-pyrazine by the method described in J.Org.Chem. 27, 1363 (1962). B.p. 80C./l0 mm. Hg.

(1) k. 2-Methyl-3(5,6)-(pyrrolyl-l )-pyrazine can be prepared as follows: N-Pyrrolyl-lithium is prepared by reacting 0.242 mole (15.4 g. of butyllithium (as 15 percent suspension in hexane) with 0.22 mole 14.7 g.) of pyrrole at 20C. in the presence of 100 ml. of tetrahydrofuran. There is then added at room temperature a solution of 0.2 mole (25.6 g.) or 3(5,6)-chloro-2- methyl-pyrazine [obtained by the method described in J.Org.Chem. 26, 2356 (1961)] in 75 ml. of tetrahydro furan. The reaction mixture is refluxed for 5 days and subjected to the usual treatments for purifying and isolating the reaction product which is then distilled. There is thus obtained 2-methyl-3(5,6)-N-pyrrolylpyrazine as a fraction distilling at l20l 24C./ 1 0 Torr.

(l) l. 2-(Thienyl-2)-3methyl-pyrazine is prepared as follows. A solution of 0.36 g. (0.006 mole) of ethylene diamine in 3 ml. of ether is cooled to 0C. To this solution there is added slowly in a nitrogen atmosphere a solution of 0.94 g. (0.006 mole) of (thienyl-2) methyl diketone (obtained by oxidation of 2-propionylthiophene with selenium dioxide) in 3 ml. of absolute ether. The ether is gradually replaced by benzene, and water is removed as an azeotropic mixture with the latter solvent. The reaction product is fractionally distilled, and the fraction boiling at l05C./0.003 mm. Hg. is redistilled through a copper chromite column (GIR- DLER G-l 3) heated at 350C. There is thus obtained 2-(thienyl-2)-3-methyl-pyrazine of hp. 94C./0.03 mm. Hg.

1 q. 2-lsopropenyl-pyrazine is obtained from 2- ethyl-pyrazine by the method described in .l.Org.Chem. 27, 1363 (1962). lt has the following peaks in the MS: 119 (100 percent), 120 (81 percent) and 67 (21 percent).

(1) r. 2-Methyl-3-viny1-pyrazine is prepared from 2,3-diethylpyrazine by the same method as used for compund (1) q. It has a b.p. of 6667C./13 mm. Hg.

(2) b. 2,6-Dimethyl-3-ethyl-pyrazine is prepared by the addition of an ethyl group at the 3-position of 2,6- dimethylpyrazine by the alkyl-lithium method described by Klein at al. in J.A.C.S. '73, 2949 (1951). The resulting product has a b.p. of 64-66C./8 mm Hg.

(2) c. 2,5-Dimethyl-3-ethyl-pyrazine is prepared by the addition of an ethyl group at the 3-position of 2,5- dimethyl-pyrazine by the alkyl-lithium method described by Klein et al. (loc.cit.). The resulting product has a b.p. of 63-68C./8 mm. Hg.

(2) d. 2,5-Dimethy1-3-propyl-pyrazine is prepared by the addition of an n-propyl group at the 3-position of 2,5-dimethylpyrazine by the alkyl-lithium method described by Klein et al. (loc.cit.). The product is identified by mass spectrometry. It has a b.p. of 80C./ 10 mm. Hg.

(2) e. 2,6-Diethyl-3-methyl-pyrazine is prepared by the introduction of a methyl group into the 3-position of 2,6-diethylpyrazine by the method of Klein et a1. (loc.cit.). The product has a b.p. of 9l92C./13 mm. Hg.

2) f. 2,5-Diethyl-3-methyl-pyrazine is prepared by the introduction of a methyl group into the 3-position of 2,5-diethylpyrazine by the method of Klein et al. (loc.cit. The product was isolated by gas chromatography and was identified by mass spectrometry.

(2) g. 2,5-Dimethyl-3-butyl-pyrazine is prepared by introducing a butyl group into the 3-position of 2,5- dimethylpyrazine by the method of Klein et al. (loc.- cit.). The resulting product has a b.p. of 91C./9 mm. Hg.

(2) h. 2,3-Dimethyl--isoamyl-pyrazine is prepared by introducing an isoamyl group into the 5-position of 2,3dimethylpyrazine by the method of Klein et al. (loc.cit.). The product is identified by mass spectrometr (2) i. 2,S-Dimethyl-3-isoamyl-pyrazine is prepared by introducing an isoamyl group into the 3-position of 2,5-dimethylpyrazine by the method of Klein et al. (loc.cit.). The product has a b.p. of 120C./13 mm. Hg.

2) j. 2,3-Diethyl-S-methyl-pyrazine is prepared by the method described for the preparation of compound l a. in Group VII, using l,2-diamino-propane instead of ethylene diamine and dipropionyl as the a-diketone. The product has a b.p. of 79-80C./12 mm. Hg.

(3) i. 2Methy1-3butyl-quinoxaline is obtained by the same method as compound (3) d. of Group Vll. It has a b.p. of l53C./9 mm. Hg. (3)j. 2-Methyl-3isobutyl-quinoxaline is obtained by the same method as compound (3) e. of Group V1]. It has 21 mp. of 9495C.

(4) a. 2-Methyl-o-ethyl-pyrazine was obtained by the alkylation of 2,6-dimethyl-pyrazine by the method described by Levine and Behun in J.Org.Chem. 26, 3379 (1961). It has a boiling point of 54-57C./11 mm. Hg.

(4) c. 2,6-Diethyl-pyrazine was obtained by subjecting compound (4) a. to a second alkylation by the procedure described above. it has a boiling point of 70 at 10 mm. Hg.

(4) d. 2-Methyl-6-vinyl-pyrazine is obtained by starting with 2,6-dimethyl-pyrazine and following the method of Levine et al. reported in J.Org.Chem. 2'7, 1363 (1962). It has a b.p. of 7475/22 mm. Hg.

(5) a. 2,3,5-Trimethyl--butyl-pyrazine was prepared by introducing a butyl group into the 6-position of 2,3,5-trimethylpyrazine by the method of Klein et al. (loc.cit.). The product was isolated by gas chromatography and identified by mass spectrometry.

(5) b. 2,3,5-Trimethyl-6-isoamyl-pyrazine was prepared by introducing an isoamyl group into the 6- position of 2,3,5-trimethyl-pyrazine by the method of Klein et al. (loc.cit.). The product had a b.p. of C./10 mm. Hg.

(5) c. 2,5-Dimethyl-3,6-dipropyl-pyrazine was prepared by first forming 3-oximino-2-hexanone by reacting 2-hexanone with nitrosyl chloride according to the method of BOUVEAULT, Bull. [3 31, 1163 (1904). The autocondensation of two molecules of the iminoketone in the presence of zinc and acetic acid [according to the method described in Chimia l 1, 310 7)] yielded 2,5-dimethyl-3,6-dipropyl-pyrazine which had a b.p. of 1091 10C./10 mm. Hg.

(5) d. 2,5-Dimethyl-3,6-diisopropyl-pyrazine was prepared by first forming 4-methyl-3-oximino-2- pentanone by reacting 4-methyl-2-pentanone with nitrosyl chloride according to the method of BOU- VEAULT, Bull. [3 31, 1163 (1904). The autocondensation of two moles of the imino-ketone in the presence of zino and acetic acid [according to the method described in Chimia 11, 310 (1957)] yielded 2,5- Dimethyl-3,6-diisopropyl-pyrazine which had a b.p. of 91C./8 mm. Hg.

(5) e. 2,5-Dimethyl-3,-dibutyl-pyrazine was prepared by first forming 3-oximino-2-heptanone by reacting 2-heptanone with nitrosyl chloride according to the method of BOUVEAULT, Bull. [3 31, 1163 (1904). The autocondensation of two moles of the iminoketone in the presence of zinc and acetic acid [according to the method described in Chimia 1 1, 310 1957)] yielded 2,5-dimethyl-3,6-pyrazine which had a b.p. of 18C./0.002 mm. Hg.

(5) f. 2,5-Dimethyl-3,o-diisobutyl-pyrazine was prepared by first forming 5-methyl-3-oximino-2-hexanone by reacting 5-methyl-2-hexanone with nitrosyl chloride according to the method of BOUVEAULT (loc.cit.). The autocondensatione of two moles of the iminoketone in the presence of zinc and acetic acid [according to the method described in Chimia 1 1, 310 (1957)] yielded 2,5-dimethyl-3,6diisobutyl-pyrazine which had a b.p. of 6970C./0.01 mm. Hg.

(5) g. 2,5-Dimethyl-3,6-diamyl-pyrazine was prepared by first forming 3-oximino-2-octanone by reacting 2-octanone with nitrosyl chloride according to the method of BOUVEAULT 1oc.cit.). The autocondensation of two moles of the imino-ketone in the presence of zinc and acetic acid [according to the method described in Chimia 11, 310 (1957)] yielded 2,5- dimethyl-3,6diamyl-pyrazine which had a b.p. of 78C./0.03 mm. Hg.

5) h. 2,5-Dimethyl-3,o-dihexyl-pyrazine was prepared by first forming 3-oximino-2-nonanone by reacting 2-nonanone with nitrosyl chloride according to the method of BOUVEAULT (loc.cit.). The autocondensation of two moles of the imino-ketone in the presence of zinc and acetic acid [according to the method described in Chimia 1 1, 310 (1957)] yielded 2,5-

dimethyl-3,6-dihexyl-pyrazine which had a b.p. of

112120C./0.01 mm. Hg.

(5) i. 2,3,5-Trimethyl-6-hexyl-pyrazine was prepared by introducing a hexyl group into the 6-position of 2,3,5-trimethylpyrazine by the method of Klein et al. (1oc.cit. The product had a b.p. of 89-91C./O.2 mm. Hg.

(5) j. 2,5-Dimethyl-3,6-diethyl-pyrazine is prepared by alkylation of 2,5-dimethyl-3-ethyl-pyrazine accord ing to the alkyl-lithium method described by Klein et a1. [J.A.C.S. 73, 2949 (1951)]. It has a b.p. of 8385C./8 mm. Hg.

(6) a. 2-Ethyl-S-methyl-pyrazine was prepared by alkylation of 2,5-dimethyl-pyrazine following the proce dure of Levine and Behun described in .I.Org.Chem. 26, 3379 (1961 It has a boiling point of 60C./11 mm. Hg.

(6) b. 2-lsopropyl-5-methyl-pyrazine was produced in the preparation of compound (6a. as a by-product and was separated from the reaction mixture by gas chromatography. Identification was confirmed by mass spectrometry.

(6) c. 2,5-Diethyl-pyrazine was obtained by subjecting compound (6) a. to a second alkylation by the procedure given for compound (6) a. above. It boils at 64C. at 12 mm. Hg. (6) d. 2-Methyl-5-vinyl-pyrazine was prepared by the method of Levine et al. described at J. Org. Chem. 27, 1363 (1962), starting from 2,5- dimethyl-pyrazine. It has a boiling point of 6566C./12 mm. Hg.

Vlll. Aliphatic and Aromatic Alcohols This group comprises compounds having the general formula:

benzyl isoamyl carbinol benzyl hexyl carbinol 1 a. n-amylalcohol c.a. b. isoamylalcohol c.a. c. n-hexanol c.a. d. n-heptanol c.a. e. n-octanol 6.21. f. n-nonanol ea. g. n-decanol c.a. h. Z-heptanol cu. i. 3-octanol c.u.

(2) a. phenylethan-l-ol c.a. h. phenylpropan-l-ol ea. c. cinnamyl alcohol (1.21. d. phenyl methyl carbinol c.a. c. benzyl methyl carbinol 0.11. f. benzyl ethyl carbinol ea. g. benzyl butyl carbinol n.c. h. benzyl amyl carbinol n. n.c

The new compounds of this Group VIII can be prepared as follows:

(2) g. Benzyl butyl carbinol. To a solution of 1.05 mole of butyl-magnesium bromide in 400 ml. of ether there is added a solution of 1 mole (120 g.) of phenylacetaldehyde in 300 ml. of ether at 8 to -12C. within 3 to 4 hours. The reaction mixture is heated to about 20C. and worked up by conventional methods. Distillation of the crude reaction product yields 99 g. of benzyl butyl carbinol of b.p. 889lC./0.06 Torr; df 0.9485; n 1.5059.

The same method is used for preparing:

(2) h. Benzyl amyl carbinol, b.p. 81C./0.01 Torr.

(2) i. Benzyl isoamyl carbinol, b.p. l42143C./13 Torr; d 0.9377; n 1.5009.

(2) j. Benzyl hexyl carbinol, b.p. C./0.01 Torr; d 0.9339; n,, 1.4997.

Organoleptic evaluation data are listed in TABLE Vlll below.

IX. Furan Ethers The compounds of this group have the general formula:

(1) l on wherein R and R are hydrogen; alkyl, e.g. methyl, ethyl; aryl, e.g. phenyl, alkylphenyl; furfuryl, or alkylfurfuryl groups. Compounds representative of this group include the following:

Ber. 56, 1004 (1923) 1) a. furfuryl methyl ether b. furfuryl efllyl ether Ber. 56, 1004 (1923) c. furfuryl phenyl ether Bull. 1938, 1 151 d. S-methyl-furfuryl n.c.

Furfuryl other e. difurfuryl ether Am.Soc. 49, 1066 (1927) X Thiophene Ethers This group of compounds are described by the structural formula:

(1) CH OR wherein R is an alkyl group, phenyl, alkylphenyl, furfuryl, alkylfurfuryl, or thenyl group, and includes for example:

( 1) a. thenyl methyl ether LACS. 49, 1066 (1927) -Continued J.A.C.S. 50, 1960 1928 hv dithenyl ether n.c. c. furfuryl thenyl ether n.c.

The new compounds of this group were prepared as follows:

(1) b. Dithenyl ether. To a suspension of 1.32 g. (0.01 mole) of chloromethylthiophene [obtained by the method of F. F. BLICKE, J.A.C.S. 64, 477 (1942)] and 1.2 g. (0.02 mole) of powdered potassium hydroxide in ml. of ether there is added a solution of 3.5 g. (0.03 mole) of thenyl alcohol in 10 ml. of ether. The reaction mixture is stirred for 1 hour at room temperature, then refluxed for 30 minutes and finally allowed to stand over night. After filtration the ethereal solution is concentrated and the residue fractionally distilled. There is obtained 0.22 g. (10 percent) of dithenyl ether having a b.p. of 99C./0.01 mm. Hg. and a m.p. of 36.5".

1 c. Furfuryl thenyl ether is obtained by the same method as used for preparing compound (1) b., but using furfuryl alcohol instead of thenyl alcohol. The product thus obtained had a b.p. of 50C./0.01 mm. Hg.

Organoleptic evaluation data on representatives of this group of compounds are set out in TABLE X below.

X1 Thiazole Alcohols Compounds of this group have the following structural formula:

R is an alkyl group, e.g., containing from 1 to 4 carbon atoms, or an alkenyl group, e.g., vinyl. Representative compounds include the following:

( 1 a. methyl (4-methyl-thia2olyl-2) carbinol n.c h. ethyl (4-methyl-thiazolyl-2) carbinol n.c c. vinyl (4 methyl thiazolyl-2) carbinol n.c d. isohutyl (4-methyl-thiazolyl-2) carbinol n.c

The new compounds of this Group X can be prepared as follows:

(1) a. Methyl (4methyl-thiazolyl2) carbinol Was preprcd by starting from 4-methyl-thiazole and substituting the hydrogen atom in the 2-position by lithium by reaction with butyllithium. The resulting metalorganic compound was reacted with acetaldehyde (of. J.A.C.S. 74, 6260 (1952)]. The resulting product has a b.p. of 102-103C./9 mm. Hg.

l bv Ethyl (4-methyl-thiazolyl-2) carbinol was prepared by starting from 4-methyl-thiazole and substituting the hydrogen atom in the 2-position by lithium by reaction with butyllithium. The resulting metal-organic compound was reacted with propionaldehyde 10f. J.A.C.S. 74, 6260 1952)]. The resulting product had a b.p. of 110l15C./9 mm. Hg. and a m.p. of 6772C.

( 1 c. Vinyl (4-mcthyl-thiazolyl2) carbinol was pre- 6 pared by starting from 4-methyl-thiazole and substituting the hydrogen atom in the 2-position by lithium by reaction with butyllithium. The resulting metal-organic X11 -Pyridine Ethers and Alcohols Compounds of this group are found to have the following general formula:

wherein R is hydrogen or an alkoxy group, R is hydrogen or an alkyl group, and n is 0, l or 2. Examples of this group include:

l a. 2-methoxy-pyridine e.a. b. 2-butoxy-pyn'dine n.c. c. Z-methoxymethyl-pyridine c.a. d. 2-methoxymethyl-6-methyl-pyridine ea c. 2-hydroxymethyl-pyridine (3.8. f. 3-hydroxymethyl-pyridine c.a. g. 4-hydroxymethyl-pyridine c.a. h. 2-hydroxymethyl-6-methyl-pyridine ea. i. 2-( 2-hydroxyethyl )-pyridine c.a. j. 2-( 2-ethoxyethyl )-pyridine 6.21.

(1) b. 2-ButoXy-pyridine was prepared according to the method described in J.A.C.S. 69, 1803 (1947) by condensing 0.17 mole of 2-bromo-pyridine with 0.195 mole of sodium butoxide. By distillation of the reaction product there were obtained 15 g. of 2-butoxy-pyridine distilling at 78C./1O mm. Hg. n,, 1.4880; df 0.9723.

Organoleptic evaluations are set out in TABLE X11 below.

Xlll Pyrazine Ethers and Alcohols Compounds of this group are represented by the general formula:

l (cu 0a wherein R represents hydrogen or an alkyl group and n is 0,

l or 2. Examples of compounds covered by this formula are:

h. Z-methoxymethyl-pyrazine e. Z-ethoxymethyl-pyrazine Compounds l b. and l c. were prepared by reacting 2chloromethyl-pyrazine with the corresponding sodium alkoxide according to the same method as used for the preparation of sulfides [cf. HOUBEN-WEYL,

19 20 4th edition, vol. 9, 97 (1955)]. The products thus obwherein tained had the following boiling points: R is alkyl, furfuryl or thenyl group.

compound (1) b.: 51C./8 mm. Hg; Representative compounds include, for example:

compound (1) c.: 75C./8 mm. Hg. Organoleptic evaluations are set out in TABLE X111 5 b low (l) l-ethyl-pyrrole-Z-aldehyde n.c.

e b. 1 butyl-pyrrole-Z-aldehyde Helv. 13,

349 1930) XIV Benzofuran Carbonyl Compounds l-butyl-pyrrole-3-aldehyde d. l-amyl-pyrrole-Z-uldehyde n.c. This group of compounds has the following general c. 1-amyl-pyrrole-3-aldehyde n.c. f. 1-a-methylbutyl-pyrrole-Zmldehyde n.c. formula" 10 g. l-a-methylbutyl-pyrrole-3-aldehyde n.c.

h. l-furfuryl-pyrro1e-2-aldehyde Helv. 13, R 349 (1930 R2 I I i. 1-furfuryl-pyrrole-3-aldehyde n.c. 1 .0 j. l-thenyl-pyrrole-Z-aIdehyde n.c.

U k. l-isoamyl-pyrrole-2-aldehyde Helv. l3,

1 5 349 (1930) wherein R and R may be hydrogen or alkyl. Examples of compounds included in this definition The new compounds of this group XVI can be prepared as follows:

are:

l a. 1-Ethyl-pyrro1e-2-aldehyde was prepared from B n 19 2 1875 l-ethyl-pyrrole [obtained by the method described in benmfufan-z-aldehyde 6 t Helv. 10, 387 (1927)] by introducing a formaldehyde z'acetyl'benzofumn 754 group following the technique described in Org. Synth. 7-melhyl-benzofuml'l-2-aldehyde 36, 74 1956). The product boiled at 73-75C./7 mm. H

7-Methyl'benzofuran'zaldehyde was P p %1) c. l-Butyl-pyrrole-B-aldehyde was prepared by by formylating 7-methy1-benzofuran according to the h same th d as d f compound 1 It h a same method as used for the preparation of benzofub f 148 150C /1 1 H ran-2-a1dehyde. The product thus obtained has the fOl- 1 1.Amy[ pyrr le-2-aldehyde was prepared by lowing ion peaks in its mass Spectrum; 160 P the same method as used for compounds (1) a. It has cent), 159 (62 percent) and 131 (33 percent). 3 h of l11-l12C./1 1 mm. Hg.

Organoleptic evaluations are set out in TABLE XIV l e, l-Amyl-pyrr0le-3-alde hyde was prepared by below. the same method as used for compound l a. It has a b.p. of l55160C./l1 mm. Hg.

Xv Thlophene Aldehydes (1) f. l-a-Methylbutyl-pyrrole-Z-aldehyde was pre- Compounds of this group have the general formulae: d b th same ethod as d f compound (1 a. It has a b.p. of 103lO5C./ll mm. Hg. I 1) g. l-aMethylbutyl-pyrrole-3-a1dehyde was pre- 5 (mo pared by the same method as used for compound (1 40 a. It has a b.p. of l50C./l 1 mm. Hg. wherein (l) h. l-Furfuryl-pyrrole-2-aldehyde was prepared R is hydrogen, or an alkyl or thenyl group; and starting with l-furfurylpyrrole described by Reichstein in Helv. 15, 1450 (1932) as well as Gianturco et al., in Tetrahedron 20, 1763 1964). The aldehyde group was (2) 2 COR introduced by the Vilsmeyer reaction (e.g., by the s 1 method described in Bull. 1962, 1989). A small amount of the corresponding 3-aldehyde is obtained as wherein a byproduct and can be separated by fractional distilla- R and R represent hydrogen or alkyl. tion. The 2-aldehyde boils at 139-l40C./1 2 mm. Hg. Compounds in this group include for instance: and is a viscous colorless oil. The 3-aldehyde has a b.p.

(l) a. Thiophene-2-aldehyde c.a.

b. 5-methy1-thiophene-2-aldehyde OrgSyn. 36, 74 1956) c. 3-methyl-thiophene-2-aldehyde *b.p. 88-89C/10 mm.Hg. d. 5-propyl-thiophene-2-aldehyde *b.p. 6465(./().(l()2 mm.Hg. e. 5-lhenyl-thiophene-2-aldehyde *mp. 31-32%. *prepared according to the same method as used for compound l b.

(2) a. benmthiophene-2-aldehyde J.A.C.S. 74, 2935 (1952) b. 2acetyl-benzothiophene Compt.Rend.234, 736 1952) Organoleptic evaluations are set out in TABLE XV of l9()C./l2 mm. Hg.

below. (l)j. l-Thenyl-pyrrole-2aldehyde was prepared by the same method as used for compound 1 h. It has a XVI Pyrrole Aldehydes b.p. of 98C./0.005 mm. Hg. Compounds of this group have the structural formula The organoleptic evaluations are shown in TABLE XVl below.

.... GHQ

XVII Pyrazinc Carbonyl Compounds Compounds of this group have the general formula:

Representative examples of compounds in this group include: in

(CH C-R N 6 5 l) a. Z-acetyl-fum c.a. wherein b. 2-propionyl-furan J.A.C. s. 72. 3695 (1950) c. 2-butyryl-furan J.A.C.S. 72. 3695 (1950) R is hydrogen or an alkyl group and n is or I. I A C.S. 72, 3695 (1950) Examples of this group include: e. S-methyl-Z-acetyl-furan .I.A.C.S. 72, 3695 (1950) f. 5-methyl-2-propionyl- J.A.C.S. 72. 3695 (l950) furan g. furfuryl methyl ketone Ber. 76, 192 (19430 y -py CA- 10180!) 1963) h. furfuryl ethyl ketone J. Org.Chem. l5. 8 (1950) b. Z-acetyl-pyrazine J.A.C.S. 74. 3621. (1952) i. (S-methyl-furfuryl) n.c. c. 2-acetonyl-pyrazine J.Org.Chem. 23. 406 I958) methyl ketone j. (S-methyl-furfuryl) ethyl n.c. ketone Organoleptic evaluations are tabulated in TABLE 4 fury| 2 bummne LACS 72, 3695 (1950) XVII below. l. 4-(5-methylfuryl)-2- Ber. 76, 192 (l943) butanone XVIII Aliphatic and Aromatic Ketones l-(5mefllylfuryn'3' pentanone The compounds of this group are defined by the following general formula: The new compounds of this group can be prepared as follows: CO R2 l i. (S-Methyl-furfuryl) methyl ketone was pre- 1. pared according to the procedure described by Hass et h i al., in J.Org.Chem. 15, 8 (1950) by condensing R is an alkyl group having from 1 to 3 carbon atoms ylf ryll ehy With nitroethane. The

and R is an alkyl group having from 3 to l 1 carbon Product has a -P- of 8- at m o a h l o b l group, (l) j. (S-Methyl-furfuryl) ethyl ketone was prepared Examples of compounds corresponding to this definiby the Same method as used for compound ti are as f ll cept that l-nitropropane was used instead of nitroethane. The product has a b.p. of 97lOOC./l5 mm. Hg. (l) m. l-(S-Methylfuryl)-3-pentanone was prepared 1 a. methyl amyl ketone by the method described in Ber. 76, 192 1943). It has b. methyl hexyl ketone ca. 0 a c. methyl heptyl ketone ea. 3 -P 101 C-/1 1 gmethyl 3' ketone Organoleptic evaluation data are set out in TABLE 0. methyl iionyl ketone c.a. XIX b l f. methyl decyl ketone 0.11. e g. methyl undecyl ketone ca. hv ethyl hutyl ketone c.a. XX Thiophene Ketones i. ethyl amyl ketone c.a. j. dipropyl ketone ea. Compounds of this group which have been found to k. propyl isopropyl ketone J.A.C.S. 63. 3l63 (194]) L p py kamne JvA-C'S 59. I926 1937) have utility in the concept of the instant invention have ucemphenone CA the following general formulae: nv propiophenone ca. 40 o. isopropyl phenyl ketone c.a. R I p. methyl benzyl ketone ca. q. ethyl benzyl ketone c.2i. (l) l f (CH2) -C-R2 n II S O Organoleptic evaluations are tabulated in TABLE bClOW. wherein XIX Furan Ketones n is O or 1. R is hydrogen or alkyl and R is alkyl; and

This family of compounds have the following general I I formula:

I I (CH cocii I I CH C 3 S (1) (cu -c-n 3 2 n n 2 *1 0 wherein n is 0 or 1. Whercm 5S Representative compounds include:

(I i a. Z-ucctyl-thiophcne J.A.C.S. 72. 3695 1950) h. 3-mcthyl-2-acetyl-thiophcnc J.A.C.S. 72. 3695 (1950) c. 4-mcthyl-2-acctylthiophenc J.A.C.S. 72. 3695 (1950 d. 3-mcthyl-2-propionyl-thiophcnc J.A.C.S. 72. 3695 (1950) c. 5-mcthyl-2-propionyl-thiophenc J.A.C.S. 72. 3695 (1950) f. Z-butyryl-thiophene J.A.C.S. 72. 3695 (1950) g. 5mcthyl-2-acctyl-thiophenc .|.A.C.S. 72. 3695 (1950) h. Z-propionyl-lhiophcnc J.A.C.S. 72, 3695 (1950) i. 2-acetylmethylthiophcne C.A. I. 105094. l957) (2) a. 5.5'-diucctyl-dithieny|-Z.2'- J.A.C.S. 73. i270 i951 methane h. 5.5 '-diacetyldithicnyl-2.2' J.A.C.S. 78. I958 H956) n is 0. l or 2 and wherein R is hdyrogen or methyl.

and R is alkyl.

Organoleptic evaluation data are set out in TABLE XX below.

XXI Pyrrole Ketones Compounds of this group have the general formulae:

X is oxygen or sulfur, R, is an alkyl group, and R is hydrogen or an alkyl group;

(2) ll N wherein R is an alkyl group;

*3 fi M2 wherein R, is hydrogen or an alkyl group and R is an alkyl group:

3 w a N wherein R R and R represent hydrogen or alkyl groups and R is an alkyl group. Compounds which are representative of this group include:

( l l-furfuryl-2-acetyl-pyrrolc 1-thenyl-2-acetyl-pyrrole 1-thenyl3-acetyI-pyrro1c l-ucctyl-pyrrole l-propionyI-pyrrole 2-methy1-5-ucetyl-pyrrole l ,Z-dimcthyI-5-acctyl-pyrrole 2,S-dimelhyl3-acctyI-pyrro1e 1 -methyI-3-acetyl-pyrrole The new compounds included in this group can be prepared as follows:

1 a. 1-FurfuryI-2-acetyl-pyrrole was prepared starting from l-furfuryl-pyrrole described by Reichstein in Helv. 15, 1450 (1932) as well as Gianturco et al. in Tetrahedron 20, 1763 1964). Acetylation by reaction of the Grignard intermediate with acetyl chloride lcf. Chem. Ber. 47, 1416 (1914)] led to the desired ketone. (A small amount of the 3-isomer was also obtained, separable by fractional distillation). The product boils at 100l02C./0.03 mm Hg. and crystallizes on standing. Recrystallization from a mixture of methylene dichloride and petroleum ether gave a'white crystalline product with a m.p. of 4243C.

(3) b. 1,Z-DimethyI-S-acetyl-pyrrole was obtained by acetylating l,2-dimethy1pyrro1e according to the method described in Ber. 47, 1416 (1914 [cf. also .I.A.C.S. 85, 2859 (1963)]. The product has a b.p. of

102106C./l0 mm. Hg.

(4) b. 1-Methyl-3-acetyl-pyrrole was obtained as a by-product in the synthesis of l-methyl-Z-acetylpyrrole according to the method described in Ber. 47, 1416 1914). The product has a b.p. of 130] 32C./1 2 mm. Hg.

Evaluation data are set out in TABLE XXI below.

XXII Thiazole Carbonyl Compounds Compounds of this group have the following general formula:

R (1) R2 J-(E-o wherein R, and R are hydrogen or alkyl groups. Representative compounds of this group are:

( 1) a. 4-methyI-2-acetyl-thiazole Bull. 20, 702 (1953) b. 4-methyl-2-propionylthiazole c. 5methyl2-acetyl-thia2ole d. 4-methyl-2 hutyryl-thiazole c. 4-methyl-2-formyl-thiazole n.c. Bull. 20, 702 (1953) The new compounds included in this group can be prepared as follows:

(1) b. 4Methyl-2-propionyl-thiazole was prepared according to the method described in Bull. 20, 702 (1953) by reacting 4-methyl-thiazole with ethylmagnesium bromide and acylating the obtained Grignard intermediate with propionyl chloride. The product has a b.p. of 8388C./9 mm. Hg.

(1) d. 4-Methyl-Z-butyryl-thiazole was prepared by the same method as compound l b, but using butyric anhydride as the acylating agent. The product has a b.p. of 110-1l5C./8 mm. Hg.

(1) e. 4-Methyl-2-formyI-thiazole was prepared by oxidizing 2-hydroxymethyl-4-methyl-thiazole with n.c. J.A.C.Sr 85,2859 (1963) J.A.C'.S. 85,2859 1963) Chem. & Ind. 1965, 1426 Her. 89. 1938 (1956) n.c. Bcilstein XXI, 277 (1935) TLC.

chromic acid in a sulfuric acid medium according to the method described in .I.A.C.S. 53, 1470 (1931). The product was identified by mass spectrometry (peaks M/e and relative intensity): 71 percent), 127 (97 percent) and 72 (48 percent).

Organoleptic evaluation data are set out in TABLE XXII below.

XXIII Pyridine Carbonyl Compounds Compounds of this group have the general formula:

wherein R represents hydrogen, an alkyl group or a phenyl group, R represents hydrogen. an alkyl group or an acyl group and n is O, l or 2. Representative compounds include:

The new compound, 4-('y-pyridyl)-butan-2-one, was prepared as follows:

8 ml. of 2-n NaOH solution were added to a mixture of 10.8 g. (0.1 mole) of pyridine-4-aldehyde, 100 ml.

of water and 10 ml. of acetone at 1215C. After a reaction time of 3 minutes the reaction mixture was neutralized with 10 percent aqueous acetic acid, saturated with NaCl and extracted with ether. After removal of the ether the residue was distilled. There were obtained 8.4 g. of 4-(y-pyridyl)-3-buten-2-one as a yellow oil of b.p. 135l38C./0.07 Torr. 5.24 g. of this product were dissolved in ml. of ethanol and hydrogenated in the presence of 4 g. of Ni-catalyst. Distillation of the reaction product yielded 4-(y-pyridyl)-butan-2-one of b.p. 83-85C./0.05 Torr; n, 1.047; n,, 1.516.

Organoleptie evaluation data are set out in TABLE XXlll below.

XXIV Alpha-Diketones Compounds of this group which have been found to have utility in the concept of this invention are of the formulae:

1 CH COCOR 2 C H COCOR wherein R is an alkyl group or a phenyl group. Compounds representative of this group include:

acctylhutyryl J. Chem. Soc. 1946, 56

due. The distillation was then continued at a bath temperature of 150l80C. After 15 ml. of distillate consisting of the reaction product and water had been collected, the flask was again cooled, and the addition of water followed by distillation were repeated several times until the reaction product was completely distilled. The combined distillates were extracted with ether, after washing the extract with aqueous sodium carbonate and water and evaporation of the solvent, the residue was distilled. There were obtained 3.9 g. of pure 5-methyl-heptan-2,3-dione distilling at 45-47C./8 Torr. n,, 1.4200; d 0.9099.

(1) g. 5-Methyl-octan-2,3-dione was prepared according to the same method as 5-methyl-heptan-2,3- dione, except that 0.5 mole of acetol, 0.55 mole of a-methyl-pentenal and 4.5 ml. of cone. HCl were used for the reaction. There were obtained 16 g. of pure 5-methyl-octan-2,3-dione distilling at 6566c./l 1 Torr; n 1.4258; df 0.9107.

(1) h. Acetylvalerianyl was prepared according to the same method as compound (1) f. It has a b.p. of 7172C./44 mm. Hg.

(1) i. Acetylheptanoyl was prepared by hydrolyzing 3-oximino-nonan-2one according to the method of Bouveault et al. described in Bull.Soc.Chim. France [3] 31, 1145 (1904). 3-Oximino-nonan-2-one was obtained by nitrosation of nonan-Z-one with ethyl nitrite according to the method described in Org.React. V11, Chap. 6 (1953). Acetylheptanoyl has a b.p. of 74C./9 mm. Hg.

(2) c. 5-Methyl-heptan-3,4-dione was prepared according to the method described in Bull [3], 31, 1 145 (1904). It has a b.p. of C./12 mm. Hg.

The organoleptic evaluations are set out in TABLE XXIV below.

XXV Thiophene Alphadiketones Compounds of this group have the following general formula:

a h. aeetylisohutyryl Ber. 2.. 2121 1889) c. acctylisovulerianyl Ber. 22, 2122 1889) d. ucctylcupmyl j.pr.Ch.|2] 58, 402 (1898) n,,*" 1.4214; (1 0.9183 c. ucctylhenzuyl 0.11. (British Drug House) 1. 5-methy1-hcptanedionc-2.3 n.c. g. 5mcthyl octancdione-2.3 n.c. h. ucetylvulcriunyl n.c. i. ucctylheptanoyl n.c. (2) u. dipropiunyl Bull. [3]. 31. 629.650 (1906) h. heptune-3A-diune Bull. [3], 31. I 174 (1904) c. 5-mcthylhcpume-3,4-dione n.c.; prepared by the method in Bull. [3], 31, 1145 1904); b.p. 55(./l2 mm. Hg.

wherein R, is hydrogen or a methyl group and wherein R is an alkyl group. Representative compounds include:

a. l-( thienyl-Z )-propanel ,2-dione n.c. h. l-( 3-methylthienyl2 )-propane 1 .2-dione n.c. c. l-(5-methyl-thienyl-2)propane-1,2 dione n.c. d. l-(thieny1-2)-butan-1,2-dione n.c.

The new compounds included in this group can be the same method as used for compound l d. of Group obtained as follows: XXV. It has a m.p. of 37-38c.

(1) a. l-('I'hienyl-2)-propane-l,2 dione was prepared Organoleptic evaluation data are set out in TABLE by acylating thiophene according to the method de- XXVI below. scribed in J.A.C.S. 72, 3695 (1950), subjecting the resulting 2-propionylthiophene to the action of nitrosyl Furan Esters chloride and hydrolyzing the reaction product in for- Compounds of this group have the general formulae: mic acid solution with nitrosyl sulfuric acid as de- 0 scribed in Bull. [3] 31, 1163 (1904). The product u formed bright yellow cyrstals and melted at 48-50C. l0

(1 b. l-( 3-methyl-thienyl-2)-propane-l ,2 dione was 0 prepared by acylating thiophene according to the wherein method described in J.A.C.S. 72, 3695(l950),subject- R is an alkyl group comprising at least 2 carbon ing the resulting 3-methyl-2-propionyl-thiophene to the atoms; action of nitrosyl chloride and hydrolizing the reaction and product in formic acid solution with nitrosyl sulfuric acid as described in Bull. 3 31, 1163 1904 The W (cu caon product had a b.p. of 93C./1l mm. Hg. 0

(l) c. 1-( S-Methyl-thienyl-Z)-propane-1,2-dione was wherein prepared by the same method as compound (1) a. It R is an alkyl or alkenyl group. has a b.p. of l50l60C. (bath temp.)/ll mm. Hg. Representative compounds of this group include:

The Furans". page 226 furfuryl propionate The Fur-ans, page 226 furfuryl hutyrate ethyl 3-(a-furyU-propionate c.a. urans". Reinhold Puhlishing Company. New York I953).

(1) d. l-(Thienyl-2)-butan-l,2-dione was prepared The new compounds included in this group can be from 2-butyryl-thiophene via the oxime accordi to 40 obtained by reacting the corresponding acid chlorides the method used in the furan series and described in with furfuryl alcohol, e.g., according to the method de- Tetrahedron 20, 2959 (1964). The product has a b.p. ri n H0ubenWeyl, fourth CCL, Vol. 8, 543 of l20123C. (bath temperature) 1 1 mm. Hg. (1952). There are thus obtained:

The organoleptic evaluations gave the results set out 1 Furfuryl iSOValerate, -P- 98C-/ l 1 in TABLE xxv below. g

(l) e. Furfuryl crotonate, b.p. 9698C./l 1 mm. Hg. XXVI Pynole Alpha'dlketones (l) g. Furfuryl a-methylbutyrate. b.p. 96C./ 1 1 mm. This group of compounds has the general formula: g-

(1) h. Furfuryl B,B-dimethylacrylate, b.p. (1) 113-115c./11 mm. Hg.

6060K; 1 i. Furfuryl valerate, b.p. 100-104c./1 1 mm. Hg. 1 N In the organoleptic evaluation tests these compounds A1 gave the results set out in TABLE XXVI] below. wherein S5 XXVlll Thiophene Esters 1 is y r g n 0r alkyl and R is alkyl. Compounds of this group have the following general Representative compounds of this group include e.g.: f l

(l) a. (pyrrolyl-2)-propan-l.Z-dione n.c.

b. (pyrrolyl-2 )-butanl .2-dione n.c.

. wherein The new compounds included in this group can be R is alkyl or furfuryl; obtained as follows: and

(l a. (Pyrrolyl-2)-propan-l ,2-dione was prepared according to the same method as used for compound 2) (1) d. of Group XXV. It has a m.p. of 5()5 1C.

(1 bv (Pyrrolyl-2)-butan-l,2-dione was prepared by 3 ,900,5 82 29 30 wherein wherein R is hydrogen or alkyl. R stands for hydrogen, hydroxy, alkoxy or alkyl and Representative compounds of this group include: R represents h d or lk l;

(cu -S-R methyl thiophene-Z-carboxylate J.A.C.S. 77. 6709 1955) ethyl thiophene-2-carboxylute J.A.C.S. 77, 6709 1955) propyl thiophene-Z-curboxylate J.A.C.S. 77. 6709 (1955) (2) R butyl thiophene-2-curboxylatc J.A.C1S. 77, 6709 (1955) 2 isoamyl thiophene-2-curboxylate no furfuryl thiophene-Z-carboxylate n.c.

thenyl formate n.c.

thenyl acetate n.c.

wherein R, stands for hydrogen. hydroxy, alkyl or alkoxy, R

The new compounds included in sub-class l) of this y be y g or alkyl, 3 represents alkyl group can be obtained by reacting thionyl chloride with benzyl and n is O, 1 or and the corresponding alkoxides according to the method described in J.A.C.S. 77, 6709 1955). There were thus obtained:

1 e. lsoamyl thiophene-Z-carboxylate, hp. (3) 7980C./O.3 mm. Hg.

1 f. Furfuryl thiophene-Z-carboxylate, b.p. 109C./0.07 mm. Hg.

The new compounds included in sub-class (2) of this group can be obtained by acylation of 2-theny1 alcohol wherein which is prepared by reducing thiophene-Z-aldehyde R stands for alkyl or phenyl. according to the method described in J. Org. Chem. 15, Representative compounds include: 790 1950). Acylation with the mixed anhydride or formic and acetic acids according to the method described in J.A.C.S. 64, 1583 (1942) yields (2) a. Thenyl formate, b.p. 8788C./15 mm. Hg. Acylation with acetic anhydride yields (2) b. Thenyl acetate, b.p. 91C./12 mm. Hg. (1)

a. 2-methnxy benzenethiol Ber. 39, 1348 1906) In the organoleptic evaluation test these compounds g i j fg hem] Bcflstefiifl 793 gave the results set out in TABLE XXVlll below. 31

e. 3methyl-ben2enethiol c.21. XXIX P rldme Esters r. 4-meth Lhenenethiol c.a.

y 24d' thlb th'l Be "12 1147 g. .-|me yene 10 r. Compounds of this group are of the general formula h. 3 4dimethyl-benzenethlol J.Org.Chem.26. 4047 (1961) 40 i. 2-ethyl-benzenethiol Ber. 59, 349

j. 2-ethoxy-bcnzenothiol J.pr.Ch. 1 14, 231, 235 a k. 4-methoxy-belnzelnettlhiol c.a. (2) a. methyl pheny su l e (1.21. (1) l l m i b, dibenzyl sulfide J.Chem.Soc. 1922. 1404 (3) a. phenyl methyl disulfide J.A.C.S. 85, 1618 (1963) b. diphenyl disulfide Ber. 56 1929 (1923) wherein R stands for lower alkyl and n is O or 1. Representative compounds of this group include:

( a. methyl (py y a Evaluation test data are set out in TABLE XXX beh. methyl (pyridy1-3)-acetate ca 1 c. methyl (pyridyl-4)-acetate c.a. d. ethyl (pyridyl-2)-acetate cxa. e. ethyl (pyridyl-IU-acetate ca XXX] Furan Sulfur Compounds 1". ethyl (pyridyl-4)-ucetatc c.a.

Compounds of this group are included in the formu- Organoleptic evaluation data are set out in TABLE lae: XXIX below.

XXX Aromatic Sulfur Compounds Compounds of this group are of the general formu- (I) I I g lae: -3-l3-R wherein u) R may be hydrogen, alkyl or alkenyl and n stands for a .E l

1 i (CH n 0 (a) E ll L wherein R is alkyl or furfuryl;

CH -S-S- R wherein R represents hydrogen or alkyl and R stands for alkyl or furfuryl; and

wherein R represents an alkyl or an acyl group. Representative compounds in this group include:

(l) g. Furfurylthiol formate was prepared according to the method used for the synthesis of furfuryl formate and described in J.A.C.S. 64, 1583 (1942). The product had a b.p. of 7778C./8 mm. Hg.

(1) h. 2-(Furyl-2)-ethanthiol acetate was prepared by reacting thioacetic acid with 2-vinyl-furane under the action of UV light and in the presence of benzoyl peroxide according to the method described in J. Org. Chem. 27, 2853 (1962). The thio-ester, after isolation by distillation had a b.p. of 100lO3C./0.05 mm. Hg.

(2) a. 5-Methylfurfuryl methyl sulfide was prepared by reacting S-methylfurfuryl-mercaptan with dimethyl sulfate in alkaline solution according to known methods. 5-Methylfurfury1-mercaptan was obtained from the corresponding alcohol by the method described in Org. Syn. 35, 67 1955). The product is a colorless liquid boiling at 7172C./l 1 mm. Hg.

(2) b. Furfuryl propyl sulfide was prepared by reacting sodium furfurylmercaptide with n-propyl bromide according to the method described in Houben-Weyl, fourth ed., vol. 9, 97 (1955). The product has a b.p. of 91C./15 mm. Hg.

(2) c. Furfuryl isopropyl sulfide was prepared by the same method as used for compound (2) b., except that isopropyl bromide was used instead of n-propyl bromide. The product has a b.p. of 84C./l6 mm. Hg.

(2) d. Furfuryl S-methylfuryl sulfide was prepared according to the method used for the synthesis of alkylthio-furans and described in C.A. 59, 8681d (1963). 2-Methylfuran was reacted with butyl-lithium and then with sulfur. The resulting thiol was further reacted (without prior isolation) with furfuryl chloride. The

The new compounds included in this group XXXl can be obtained as follows:

I a. Furfurylthiol acetate was prepared by reacting acetic chloride or anhydride with furfurylmercaptan according to the method described in Houben-Weyl, fourth ed., vol. 9, 753 (1955). The product has a b.p. of 9092C./12 mm. Hg.

According to the same method, but starting from the corresponding acid chloride or anhydride, the following products were obtained:

(1) b. Furfurylthiol propionate, b.p. 9597C./ 10

mm. Hg.

(1) c. Furfurylthiol butyrate, b.p. lO5.5106.5/10

mm. Hg.

(1) d. Furfurylthiol furoate, b.p. 110C./0.0l mm. Hg.

(1) c. Furfurylthiol B,B-dimethylacrylate, b.p.

85C./0.0l5 mm. Hg.

(1) f. Furfurylthiol tiglate, b.p. 84.587.5C./().()3 mm. Hg.

product was a slightly yellowish oil having a b.p. of 67C./0.040.05 mm. Hg.

(2) e. Methyl S-methylfuryl sulfide was prepared by the same method as used for compound (2) d. The product was a light yellow liquid having a b.p. of C./45-5O mm. Hg.

(2) f. 2-(Furyl-2)-ethanethiol was prepared by saponifying 24 g. of 2-furylethanethiol acetate with alkali in aqueous-alcoholic medium. After refluxing for minutes the reaction mixture was neutralized with acetic acid and then extracted with ether. Upon distillation there were obtained 14.4 g. of 2-(furyl-2)- ethanethiol having a b.p. of 6l62C./0.03 mm. Hg; n 1.5653; df L153 (3) a. Methylthiol fuorate was prepared by reacting furoyl chloride with methylmercaptan according to the method described in Houben-Weyl, fourth ed., vol. 9, 753 (1955). It has a b.p. of 9293C./1l mm. Hg.

(5) a. Benzofurfuryl-Z methyl sulfide was prepared by reacting (benzofurfuryl-Z )-mercaptan with dimethyl sulfate in alkaline solution. The sulfide thus obtained has a b.p. of l08l09C./O.4 mm. Hg.

The starting (benZofurfuryl-2)-mercaptan was obtained from the corresponding alcohol according to the method described in Org. Synth. 35, 67 (1955).

(5) b. (Benzofurfuryl-2)-thiol acetate was prepared by the same method as used for compound (1) a. (furfurylthiol acetate). The product has a b.p. of 120-122c./0.s mm. Hg.

Evaluation test data are set out in TABLE XXXI below.

XXXIl Thiophene Sulfur Compounds This group comprises compounds corresponding to the following general formulae:

i i (CH Sit wherein R represents hydrogen, alkyl, acetyl or thenyl, and n is 1 r 2; and

O (2) l l] g wherein R stands for alkyl or furfuryl. Specific examples of compounds corresponding to these formulae include:

(1 'a. thcnyl-mercaptan Compt.rend. 229,

l343 (1949) b. thenyl methyl sulfide Compt. rend. 229.

1343 (l949) c. thenylthiol acetate n.c. d. 2-(thienyl-2)-ethanethiol n.c. e. 2-(thienyl-Ztethanethiol acetate n.c. f. dithenyl sulfide n.c.

(2) a. thiothenoic acid S-methyl ester n.c. b. thiothenoic acid Sethyl ester n.c. c. thiothenoic acid Sfurfuryl ester n.c.

The new compounds of this group can be obtained as follows:

l c. Thenylthiol acetate was prepared by the same method as used for compound (1 a. (furfurylthiol acetate) of Group XXXl above. The product is a colorless liquid having a b.p. of ll3l 14C.

(I) d. 2-(Thienyl-2)-ethanethiol. Z-Vinyl-thiophene [obtained by the method described in Org. Synth. 38, 86 1958)] was reacted with thioacetic acid according to the method described in J. Org. Chem. 27, 2853 (1962), and the resulting addition product was subjected to hydrolysis with an acid. The product has a b.p. of 55C./O.l mm. Hg.

l e. 2-(Thienyl-2)-ethanethiol acetate was obtained as the intermediate product obtained by reacting 2-vinyl-thiophene with thioacetic acid in the preparation of compound l d. above. The produce has a b.p. of 90C./0.07 mm. Hg.

(l) f. Dithenyl sulfide was prepared by the same method as used for compound (1) b. (dithenyl ether) of Group X above, except that thenylmercaptan was used instead of thenyl alcohol. The product has a b.p. of ll8C./0.04 mm. Hg.

Compounds (2) a, (2) b. and (2) c. were prepared by reacting thionyl chloride with the sodium salts of the corresponding mercaptans in alcoholic solution according to the method described in J.C.A.S. 77, 6709 (1955). After refluxing for 1 hour the reaction mixture was filtered and concentrated. The residue was purified by chromatography on a silica-gel column using a benzene-hexane mixture 8:2 as the eluant. The structure of the resulting products was identified by mass spectrometry:

(2) a. Thiothenoic acid S-methyl ester: lon peaks with relative intensities: l l l (100 percent), 39 (22 percent) and 158 (12 percent).

(2) b. Thiothenoic acid S- ethyl ester: Ion peaks with relative intensities: ll 1 (100 percent), 39 (17 percent) and 172 (10 percent).

(2) c. Thiothenoic acid S-furfuryl ester: Ion peaks with relative intensities: 111 (100 percent), 81 (73.5 percent) and 39 (20 percent).

Organoleptic evaluation data are set out in TABLE XXXll below.

XXXIII Pyridine Sulfur Compounds The compounds included in this group have the general formula:

l J ww sr:

wherein R stands for hydrogen, alkyl, acyl or pyridyl, and n is O or 1. As examples there can be mentioned:

26, 82 (1961) h. 2-(pyridyl*2)-ethyl methyl sulfide see below i. 2-(pyridyl-2)ethyl ethyl sulfide n.c. j. 2-(pyridyl-2)ethanethiol acetate see below l. (pyridyl-2)-methyl methyl sulfide Helv. 47, 1754 m. (pyridyl-2)-methyl ethyl sulfide n.c.

n. (pyridyl-2)-methanethiol acetate n.c.

The method used for preparing the known compound (1) h. [2-(pyridyl-2)-ethyl methyl sulfide] was as follows: 2-Vinylpyridine was reacted with methylmercaptan by the action of UV light in the presence of trace amounts of benzoyl peroxide and diphenyl sulfide. The product has a b.p. of 48C./0.03 mm. Hg.

The same method was used for preparing the known compound (1) j., except that thioacetic acid was used instead of methylmercaptan. The product has a b.p. of C./0.02 mm. Hg.

The new compounds included in this Group XXXlIl can be obtained as follows:

l c. Z-Methylthio-pyridine was prepared according to the method described in Houben-Weyl, fourth ed.,

35 vol. 9, 7 1955) by alkylating 2-mercapto-pyridine with methyl halide. The resulting pyridinium salt was neutralized with NaOH and the base thus obtained ex tracted and distilled. The product had a b.p. of 67-68C./10 mm. Hg.

1) d. 2-Ethylthio-pyridine was prepared by the same method as used for compound (1) c., except that ethyl halide was used instead of methyl halide. The product had a b.p. of 7777.5C./8 mm. Hg.

(1) e. (Pyridyl-2)-thiol acetate was prepared by reacting acetic anhydride with 2-mercaptopyridine in alkaline medium according to the method described in Houben-Weyl, fourth ed., vol. 9, 753 (1955) and in J.A.C.S. 59, 1089 (1937). The product has a b.p. of ll7-1l8C./9 mm. Hg.

(1) i. 2-(Pyridyl-2)-ethyl ethyl sulfide was prepared by the same method as used for compound (1) h., except that ethylmercaptan was used instead of methylmercaptan. The product has a b.p. of 62C./0.005 mm. Hg.

(1 m. (Pyridyl-2)-methyl ethyl sulfide was prepared by the same method as used for compound (1) 1. The product has a b.p. of 107l lC./1O mm. Hg.

l n. (Pyridyl-2 )-methanethiol acetate was prepared by reacting acetyl chloride with 2-mercaptomethylpyridine in alkaline medium. The product has a b.p. of 102-l03C./9 mm. Hg.

Evaluation test data are reported in TABLE XXXIII below.

XXXIV Pyrrole Sulfur Compounds These sulfur compounds correspond to the following general formula:

(1) CH SR wherein R represents alkyl, furfuryl or acyl. As examples,

there can be mentioned:

(1 a. N-methyl-pyrryl-Z methyl sulfide n.c. b. N-methyl-pyrryl-Z ethyl sulfide n.c. c. N-methyl-pyrryl-Z furfuryl sulfide n.c. d. (N-methyl-pyrryl-Z )-methylthiol acetate n.c.

The new compounds included in this Group XXXIV can be obtained as follows:

1 a. N-Methyl-pyrryl-Z methyl sulfide was prepared by alkylating of N-methyl-(pyrryl-Z)-methylmercaptan with methyl iodide according to the method described in Houben-Weyl, fourth ed., vol. 9, 97 (1955). The product has a b.p. of 90C./10 mm. Hg.

(1) b. N-Methyl-pyrryl-Z ethyl sulfide was prepared by the same method as used for compound (1) a., except that ethyl bromide was used in place of methyl iodide. The product has a b.p. of 99C./1O mm. Hg.

1 c. N-Methyl-pyrryl-2 furfuryl sulfide was prepared by the same method as used for compound (1 21., except that furfuryl chloride was used in place of methyl iodide. The product has a b.p. of 94C./0.01 mm. Hg.

(1) d. (N-Methyl-pyrryl-Z)-methylthiol acetate was prepared by acylating (N-methyl-pyrryl-2)- methylmercaptan according to the method described in 36 Houben-Weyl, fourth ed., vol. 9, 753 (1958). The product has a b.p. of 69C./0.05 mm. Hg.

Evaluation test data are set out in TABLE XXXIV below.

XXXV Pyrazine Sulfur Compounds The compounds of this group can be represented by the following general formulae:

wherein n is 0, l or 2, R represents hydrogen, alkyl, acyl or furfuryl and R stands for hydrogen or methyl with the proviso that R and R cannot both be methyl if n is 0;

CH N 8-1! wherein R stands for hydrogen, alkyl, furfuryl or acyl. Illustrative examples of compounds corresponding to formulae (1) and (2) include:

(1) a. (2-methylpyrazinyl-3, -5 and -6) furfuryl sulfide n.c.

b. pyrazinylmethyl'mercaptan n.c. c. pyrazinylmethyl methyl sulfide n.c. d. pyrazinylmethyl ethyl sulfide n.c. e. pyrazinylmethyl furfuryl sulfide n.c. f. pyrazinylmethylthiol acetate n.c. g. Z-pyrazinyl-ethyl mercaptan n.c. h. 2-pyrazinyl-ethyl methyl sulfide n.c. i. 2-pyrazinyl-ethyl ethyl sulfide n.c. j. 2-pyrazinyl-ethyl furfuryl sulfide n.c. k. 2-pyrazinyl-ethylthiol acetate n.c.

( 2) a. 2,5-dimethyl-3mercapto-pyrazine n.c. b. 2,5-dimethyl-3-methylthio-pyrazine n.c. c. 2,5-dimethyl-3-ethylthio-pyrazine n.c. e. 2,5-dimethyL3-acetylthio pyra.zine n.c. d. 2,5-dimethyl3-fi1rfurylthio pyrazine n.c.

The new compounds included in this group can be obtained as follows:

(1) a. (2-Methylpyrazinyl-3, -5 and -6) furfuryl sulfide (mixture): A mixture of 2-methyl-3-, 5- and 6- chloropyrazine was prepared by chlorination of 2- methylpyrazine according to the method described in J. Org. Chem. 26, 2356, 2360 (1961). 0.2 Mole of the above 2-methyl-chloropyrazine mixture was added to 0.2 mole of a sodium furfurylmercaptide suspension in 250 ml. of xylene. The mixture was boiled for 6 hours. After cooling 250 ml. of water were added, the organic layer was concentrated and distilled. 13.5 g. of a mixture of (2-methylpyrazinyl-3, -5 and -6) furfuryl sulfide were obtained; b.p. l53-156C./10 Torr; n,, 1.5970; d 1.2164.

l b. Pyrazinylmethylmercaptan: a solution of 6.3 g. (0.05 mole) of chloromethylpyrazine [obtained according to the method described in J. Org. Chem. 26, 2356 i961 in 20 ml. of ether was added slowly, with stirring, to a solution of sodium hydrogensulfide percent) in 50 ml. of absolute methanol. Stirring of the reaction mixture at room temperature was continued for 3 hours. The precipitate which had formed was removed by filtering, the solvents were evaporated, and the residue was dissolved in water. The solution was extracted twice with ether. The aqueous phase was neutralized with acetic acid and extracted with ether. After drying of the extract the solvent was evaporated and the residue distilled. 0.25 g. of pyrazinylmethylmercaptan boiling at 4445C./0.07 mm. Hg. was obtained.

(1) c. Pyrazinylmethyl methyl sulfide was prepared according to the method described in Houben-Weyl, fourth ed., vol. 9, 97 (1955) by reacting chloromethylpyrazine [obtained by the method described in J. Org. Chem. 26, 2356 (1961)] with sodium methylmercaptide. The product has a b.p. of l05-l06C./l2 mm. Hg.

(1) d. Pyrazinylmethyl ethyl sulfide was prepared by the same method as used for compound (1) c., except that sodium ethylmercaptide was used in place of sodium methylmercaptide. The product has a b.p. of ll4l l6C./l2 mm. Hg.

(1) e. Pyrazinylmethyl furfuryl sulfide was prepared by the same method as used for compound (1) 0., except that sodium furfurylmercaptide was used instead of sodium methylmercaptide. The product has a b.p. of l16C./0.05 mm. Hg.

(1) f. Pyrazinylmethylthiol acetate was prepared by acetylation of pyrazinylmethylthiol according to the method described in Houben-Weyl, fourth ed., vol. 9, 753 (1955). The product has a b.p. of 52C./0.02 mm. Hg.

(1) g. 2-Pyrazinyl-ethyl mercaptan was prepared be reacting vinylpyrazine [obtained by the method described in J. Org. Chem. 27, 1363 (1962)] and hydrolyzing the resulting thiolic acid ester according to the method described in J. Org. Chem. 22, 980 (1957). The product has a b.p. of 56.560C./0.003 mm. Hg.

(1) h. 2-Pyrazinyl-ethyl methyl sulfide was prepared by reacting vinylpyrazine [c.f. J. Org. Chem. 27, 1363 (1962)] with methylmercaptan by the action of ultra violet light and in the presence of benzoyl peroxide by the method described in Acta Chem. Scand. 8, 295 1954). The product was identified by mass spectrometry. It has a b.p. of 5769C. at 0.05 mm. Hg.

l i. Z-Pyrazinyl-ethyl ethyl sulfide was prepared by the method used for compound (1) h., but using ethylmercaptan. It has a b.p. of 75C./0.03 mm. Hg.

l j. 2-Pyrazinyl-ethyl furfuryl sulfide was prepared by the method used for compound l) h., but using furfuralmercaptan. The product has a b.p. of

ll6-l l7C./0.0l mm. Hg.

1 k. 2-Pyrazinyl-ethylthiol acetate was prepared by reacting vinylpyrazine with thioacetic acid in the presence of benzoyl peroxide as a catalyst according to the method described in J. Org. Chem. 27, 2853 (1962). The product has a b.p. of 80C./0.02 mm. Hg.

(2) a. 2,3-Dimethyl-3-mercapto-pyrazine: A solution of 1.3 g. (0.023 mole) of sodium hydrogensulfide and moval of the alcohol by distillation the residue was dissolved in water and the sulfide was extracted with ether and distilled. The product (yield 75.6 percent) has a b.p. of 4050C./ll mm. Hg.

(2) c. 2,5-Dimethyl-3-ethylthio-pyrazine was prepared in the same manner as compound (2) b., except that 0.06 mole of ethylmercaptan was used instead of methylmercaptan. The product (yield 75 percent) has a b.p.-of 128C./9 mm. Hg.

(2) d. 2,5-Dimethyl-3-furfurylthio-pyrazine was prepared in the same manner as compound (2) b., except that 0.06 mole of furfurylmercaptan was used instead of methylmercaptan. The product (yield 75 percent) has a b.p. of ll20C./0.02 mm. Hg.

(2) e. 2,5-Dimethyl-3-acetylthio-pyrazine was prepared by acetylating 2,5-dimethyl-3-mercapto-pyrazine [compound (2) a.] with acetic anhydride in an alkaline medium according to the method described in Houben- 2.5 g. (0.01 mole) of 2,5-dimethyl 3-iodo-pyrazine in 70 ml. of absolute methanol was refluxed for 3 hours. After evaporation of the alcohol the residue was dissolved in l-n NaOH, the solution was filtered and the filtrate was neutralized with acetic acid. After isolation by the usual treatments the reaction product was sublimated. There was obtained 0.81 g. of a yellow powder having a m.p. of 182-185C.

(2) b. 2,5-Dimethyl-3-methylthio-pyrazine: 2.85 g. (0.02 mole) of 2,5-dimethyl-3-chloropyrazine and 0.06 mole of methylmercaptan were dissolved in a solution of 0.7 g. of sodium in 20 ml. of absolute ethanol. The reaction mixture was refluxed for 45 minutes. After re- Weyl, fourth ed., vol. 9, 753 (1955). The product has a m.p. of 36242C.

Organoleptic evaluation test data are reported in TABLE XXXV below.

XXXVI Phenols and Phenol 'Ethers The compounds of this group can be represented by the following general formulae:

wherein R represents alkyl or acetyl and R represents hydrogen or methyl, with the proviso that R and R together comprise at least 2 carbon atoms;

CH CH wherein R represents alkyl.

Examples of compounds defined by the above formulae:

( and (3) include: a. Z-ethyl-phenol b. 3-ethyl-phenol c. 4-ethyl-phenol d. 4-isopropyl-phenol c.a. Compt.rend. 177, 

1. A COMPOSITION SELECTED FROM THE GROUP CONSISTING OF FOODSTUFFS AN BEVERAGES TO WHICH HAS BEEN ADDED AN EFFECTIVE, FLAVOR IMPROVING AMOUNT OF A PYRONE OF THE FORMULA:
 2. The composition of claim 1 wherein the added pyrone is 2,6-dimethyl-gamma-pyrone.
 3. The composition of claim 1 wherein the added pyrone is 2,6-dimethyl-thio-gamma-pyrone.
 4. The composition of claim 1 wherein the added pyrone is 2,6-dimethyl-dithio-gamma-pyrone.
 5. A process for the alteration of the flavor of a composition selected from the group consisting of foodstuffs and beverages which comprises adding thereto a minor, but effective flavor modifying amount of a pyrone of the formula:
 6. The process of claim 5 wherein the added pyrone is 2,6-dimethyl-gamma-pyrone.
 7. The process of claim 5 wherein the added pyrone is 2,6-dimethyl-thio-gamma-pyrone.
 8. The process of claim 5 wherein the added pyrone is 2,6-dimethyl-dithio-gamma-pyrone.
 9. As a new composition of matter, soluble coffee to which has been added a minor, but effective flavor-modifying amount of a pyrone of the formula:
 10. Soluble coffee of claim 9 wherein the added pyrone is 2,6-dimethyl-gamma-pyrone.
 11. Soluble coffee of claim 9 wherein the added pyrone is 2,6-dimethyl-thio-gamma-pyrone.
 12. Soluble coffee of claim 9 wherein the added pyrone is 2,6-dimethyl-dithio-gamma-pyrone.
 13. A process for the alteration of the natural flavor of soluble coffee which comprises adding thereto a minor, but effective flavor modifying amount of a pyrone of the formula:
 14. The process of claim 13 wherein the added pyrone is 2,6-dimethyl-gamma-pyrone.
 15. The process of claim 13 wherein the added pyrone is 2,6-dimethyl-thio-gamma-pyrone.
 16. The process of claim 13 wherein the added pyrone is 2,6-dimethyl-dithio-gamma-pyrone. 